Side chain liquid crystalline golysiloxanes conta ing biphenyl and benzyl ether mesogen were synthesized by the hydrosilation of poly(methylhydrcsiloxane) with 4-(4-allyloxybenzytoxy)-4'- methoxybiphenyl(M_1),4-(4...Side chain liquid crystalline golysiloxanes conta ing biphenyl and benzyl ether mesogen were synthesized by the hydrosilation of poly(methylhydrcsiloxane) with 4-(4-allyloxybenzytoxy)-4'- methoxybiphenyl(M_1),4-(4-allyloxybenzyloxy)-4'-ethoxybiphenyl(M_2),4-(4-allyloxybenzyloxy)-4'- propoxybiphenyl(M_3),4-(4-allyloxybenzyloxy)-4'-butoxybiphenyl(M_4),4-(4-allyloxybenzyloxy)-4'- pentyloxybiphenyl(M_5).The phase behavior of monomeric and polymeric liquid crystals was chararcterized by differential scanning calorimetry and optical polarization microscopy.Both the monomeric and polymeric liquid crystals exhibit liquid crystal behaviors.展开更多
A new serial chiral side-chain liquid crystal polysiloxanes containing L-Tyr structures were synthesized at room temperature. Both of them exhibited Sc phase at room temperature.
Two new stationary phases : (Ⅰ) [bikis(2,6-di-O-pentyl-3-O-hex-6O-pentyl-3-O-methyl)-β-CD-polysiloxane] and (Ⅱ) [heptkis(2,6-di-O-methyl-3-O-hex-6-enyl)-β-CD-polysiloxane] were synthesized and successfully used fo...Two new stationary phases : (Ⅰ) [bikis(2,6-di-O-pentyl-3-O-hex-6O-pentyl-3-O-methyl)-β-CD-polysiloxane] and (Ⅱ) [heptkis(2,6-di-O-methyl-3-O-hex-6-enyl)-β-CD-polysiloxane] were synthesized and successfully used for GC separation of chiral isomers.The possess high column efficiency and exhibit fine chiral separation ability.展开更多
A series of elastomers , based on NBR , polysiloxanes （PS） were prepared and characterized by tensile tests, thermogravimetry （ TG ） and differential scanning calorimetry （ DSC ）. Two kinds of vulcanizing agent,...A series of elastomers , based on NBR , polysiloxanes （PS） were prepared and characterized by tensile tests, thermogravimetry （ TG ） and differential scanning calorimetry （ DSC ）. Two kinds of vulcanizing agent, DMDBH （2,5-dimethyl- 2,5-di （ t- butyl perory ） hexane ） and DCP （ dicumylperoxide ） were used to investigate the influence of different vulcanizing agents on properties of PS/ NBR. The addition of PS to NBR was found to improve the thermal stability and decrease the tensile strength of NBR. The tensile strength decreased conshterably while the elongation at break increased obviously with the increase of PS content. The series using DMDBH as vulcanizing agent showed a higher tensile strength and elongation at break than the series using DCP as vulcanizing agent. Simultaneity the thermal stability increased with the increase of PS content.展开更多
New thermotropic chloro-bridged dinuclear palladium coordinating imine side chain liquid crystalline polysiloxanes have been synthesized. Their mesomorphic properties have been investigated by DSC, X-ray diffraction a...New thermotropic chloro-bridged dinuclear palladium coordinating imine side chain liquid crystalline polysiloxanes have been synthesized. Their mesomorphic properties have been investigated by DSC, X-ray diffraction and polarizing microscopy. The polymeric complexes show nematicdiscotic (Nd) mesophase. It is found that the temperature range of liquid crystalline state of chloro- bridged polymeric complexes is much wider than that of acetato- bridged ones and imine side chain polysiloxane. This indicates that the disc-like chloro-bridged palladium complexing units play a role as mesogen in mesophase.展开更多
A new type of β-diketone based side chain liquid crystalline polysiloxanes (DKLCP) with different length of flexible spacers and end groups have been synthesized by hydrosilation reaction. This is liquid crystal poly...A new type of β-diketone based side chain liquid crystalline polysiloxanes (DKLCP) with different length of flexible spacers and end groups have been synthesized by hydrosilation reaction. This is liquid crystal polymers (LCP) using coordinating β-diketone ligand as mesogens. The phase behaviour of DKLCP polymers was studied by differential scanning calorimetry and polarizing microscopy. X-ray diffraction investigations demonstrated that the polysiloxanes with sufficiently long flexible spacers were smectic liquid crystal polymers, while those with much shorter spacers were nematic ones.展开更多
Polyurethanes（PU） were prepared using toluene diisocyanate,polypropylene glycol,ethylene glycol, dimethylolpropionic acid and triethylamine,and a siloxane modified PU（PSU） was obtained through reaction of the PU p...Polyurethanes（PU） were prepared using toluene diisocyanate,polypropylene glycol,ethylene glycol, dimethylolpropionic acid and triethylamine,and a siloxane modified PU（PSU） was obtained through reaction of the PU prepolymers with bis（3-（1-methoxy-2-hydroxypropoxy）propyl） terminated polysiloxanes（PMTS） of different molecular weight,specifically designed for this purpose.Results showed that,with increases in molecular weight of PMTS and its content,viscosity of the final PSU latexes decreased;phase separation of the incorporated PMTS in PSU films increased;the average particle sizes of the latexes varied between 110 nm and 330 nm,and the surface tension in the final latexes was relatively constant regardless of PMTS amount and its molecular weight.It was likely that copolymerized polysiloxanes had trend to enrich on top of the film when PMTS molecular weight was around 2000 and its content above 5 wt%.In general, PMTS modified polyurethane films showed higher performance than those from unmodified waterborne polyurethane latexes.展开更多
Two kinds of side chain liquid crystalline polysiloxanes containing crown ether and benzyl ether were synthesized and characterized by optical polarization microscopy. Both the monomeric liquid crystals and polymeric ...Two kinds of side chain liquid crystalline polysiloxanes containing crown ether and benzyl ether were synthesized and characterized by optical polarization microscopy. Both the monomeric liquid crystals and polymeric liquid crystals show smectic phases.展开更多
A series of side chain liquid crystalline polysiloxanes containing either cholesteryl or cyanobiphenyl mesogenic groups were synthesized by the hydrosilylation reaction of a polysiloxane containing Si H group with a v...A series of side chain liquid crystalline polysiloxanes containing either cholesteryl or cyanobiphenyl mesogenic groups were synthesized by the hydrosilylation reaction of a polysiloxane containing Si H group with a vinyl terminated compound containing the mesogenic group. Their chemical structures were confirmed by IR, 1H NMR, and elemental analysis, Their phase behaviors were investigated by differential scanning calorimetry, optical polarizing microscope, and X ray diffraction techniques. The results show that all these polysiloxanes except PⅤ display smectic or nematic mesonorphism or both. The dependence of phase transition temperature on the rigidity of mesogenic unit. the length of spacer group, and the flexibility of Si(CH 3) 2O chain is also described.展开更多
The present paper represents the syntheses of polypropyloxymethyldithia 15-crown-5 and 18-crown-6 supported on silica and their platinum complexes. The platinum complexes are effective catalysts for the hydrosilylatio...The present paper represents the syntheses of polypropyloxymethyldithia 15-crown-5 and 18-crown-6 supported on silica and their platinum complexes. The platinum complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The influences of temperature, amount of platinum complexes used and the nature of olefins used on the catalytic activity of the complexes are also investigated in this paper.展开更多
A novel kind of multifunctional polysiloxane containing charge-transporting agent and as electro-optical chromophore has been prepared for photorefractive application. The structural characterization of this kind of p...A novel kind of multifunctional polysiloxane containing charge-transporting agent and as electro-optical chromophore has been prepared for photorefractive application. The structural characterization of this kind of polymer is presented by IR spectra and elemental analysis.展开更多
Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes have been prepared from C-60 via amination with omega-decenylamine, followed by hydrosilylation with triethoxysilane and immobi...Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes have been prepared from C-60 via amination with omega-decenylamine, followed by hydrosilylation with triethoxysilane and immobilization on fumed silica or by hydrosilylation with methyldichlorosilane and polycondensation with polydimethylsiloxanol, and then by reacting them with potassium chloroplatinite or rhodium chloride in acetone respectively under argon atmosphere. It was found that the four noble metal complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The regioselectivity of platinum complexes for styrene increases remarkably by introducing C-60 moiety. Factors influencing catalytic activity and the mechanism have been investigated.展开更多
Side chain liquid crystalline polysiloxanes containing benzyl ether linkingunits were synthesized by the hydrosilylation of poly (methylhydrosiloxane) with a series of4-(4-alkoxybenzyloxy)-4'-allyloxybiphenyl mono...Side chain liquid crystalline polysiloxanes containing benzyl ether linkingunits were synthesized by the hydrosilylation of poly (methylhydrosiloxane) with a series of4-(4-alkoxybenzyloxy)-4'-allyloxybiphenyl monomers [4-(4-methoxybenzyloxy )-4'-allyloxy-biphenyl(M_1), 4-(4-ethoxybenzyloxy)-4'-allyloxybiphenyl (M_2), 4-(4-propoxybenzyloxy)-4'-allyloxybiphenyl (M_3), 4-(4-butoxybenzyloxy)-4'-allylox(M_4), 4-(4-pentoxy-benzyloxy)-4'-allyloxybiphenyl (M_5), 4-benzyloxy-4'-allyloxybiphenyl (M_6)]. The phasebehavior of monomeric and polymeric liquid crystals was characterized by differential scan-ning calorimetry and optical polarization microscopy where the groups are ranged frommethoxy to pentoxy Both the monomeric and polymeric liquid crystals exhibit 1iquidcrystal behaviors.展开更多
A variety of mesomorphic side-chain polysiloxanes were synthesized by using hydrosilylation reaction with dicyclopentadienylplatinum(II) (DPPC) as the catalyst. The mesogenic groups are derivatives of stilbene with cy...A variety of mesomorphic side-chain polysiloxanes were synthesized by using hydrosilylation reaction with dicyclopentadienylplatinum(II) (DPPC) as the catalyst. The mesogenic groups are derivatives of stilbene with cyano or nitro tail groups. The products were characterized by DSC, X-ray diffraction and polarizing optical microscopy (POM). All the polymers were found to have relatively low T-g and can form a smectic liquid crystal phase.展开更多
The comparison between physical properties and chemical structures of several polysiloxanes was studied at initial state and upon ageings. Techniques such as densimetry, gel permeation chromatography, FTIR spectroscop...The comparison between physical properties and chemical structures of several polysiloxanes was studied at initial state and upon ageings. Techniques such as densimetry, gel permeation chromatography, FTIR spectroscopy, thermogravim- etric analysis coupled with IR spectroscopy and the new tool photo-DSC were used to give assessments of average mo- lecular weight, chemical evolution, cristallinity and thermal stability. Different types of ageing such as thermal ageing (60?C and 100?C), photo-ageing and acid vapour ageing were performed. After ageing we observed an evolution of chemical structures and physical properties for all samples. The main pathway of degradation is given for each sample. It results in oxidation, chain scission or cross-linking. Cross-linking levels are dependant on the type of ageing, the chemical structure and the initial rate of cristallinity. Cross-linking reactions are favoured after photo-ageing. Oxidation is higher for polysiloxane with aliphatic carbon chain.展开更多
Nonconventional fluorescent materials,which are nonaromatic or consist of isolated aromatic systems,have attracted extensive attention because of their aggregation-induced emission properties.The mechanism of nonconve...Nonconventional fluorescent materials,which are nonaromatic or consist of isolated aromatic systems,have attracted extensive attention because of their aggregation-induced emission properties.The mechanism of nonconventional fluorescence remains incompletely understood,hindering the prediction and modulation of its emission color.Achieving full-color tunability in such systems,particularly within elastomers,is highly challenging.Herein,fluorescent cross-linked polysiloxanes are synthesized using aliphatic amino-terminated polysiloxane and glutaraldehyde,exhibiting full-color emission that can be continuously tuned through thermal treatments within a single material system.Thermal treatment of cross-linked polysiloxanes enables precise control over the structural evolution of fluorophores from imines to 3-(2-piperidyl)pyridinium derivatives and their aggregation states.It enables the continuous and wide-range modulation of the emission color.Additionally,the intramolecular and intermolecular charge transfers of the novel unconventional fluorophore,3-(2-piperidyl)pyridinium derivatives,have been identified,which are of great significance for aggregation-induced bathochromic fluorescence.Prepared from all commercial chemicals,these cross-linked polysiloxanes show great potential for large-scale production and applications,especially as flexible fluorescent light-conversion layers and solvent-responsive smart materials.Furthermore,our research is expected to inspire the innovation of unconventional fluorophores in multiple dimensions.展开更多
Nonconventional luminescent materials have been rising stars in organic luminophores due to their intrinsic characteristics,including water-solubility,biocompatibility,and environmental friendliness and have shown pot...Nonconventional luminescent materials have been rising stars in organic luminophores due to their intrinsic characteristics,including water-solubility,biocompatibility,and environmental friendliness and have shown potential applications in diverse fields.As an indispensable branch of nonconventional luminescent materials,polysiloxanes,which consist of electron-rich auxochromic groups,have exhibited outstanding photophysical properties due to the unique silicon atoms.The flexible Si-O bonds benefit the aggregation,and the empty 3d orbitals of Si atoms can generate coordination bonds including N→Si and O→Si,altering the electron delocalization of the material and improving the luminescent purity.Herein,we review the recent progress in luminescent polysiloxanes with different topologies and discuss the challenges and perspectives.With an emphasis on the driving force for the aggregation and the mechanism of tuned emissions,the role of Si atoms played in the nonconventional luminophores is highlighted.This review may provide new insights into the design of nonconventional luminescent materials and expand their further applications in sensing,biomedicine,lighting devices,etc.展开更多
Low dielectric constant(low-k)materials are critical for advanced packaging in high-density microelectronic devices and high-frequency communication technologies.Ladder polysiloxanes,which are characterized by their u...Low dielectric constant(low-k)materials are critical for advanced packaging in high-density microelectronic devices and high-frequency communication technologies.Ladder polysiloxanes,which are characterized by their unique double-chain structure and intrinsic microporosity,offer remarkable advantages in terms of thermal stability,oxidation resistance,and dielectric performance.However,structural defects in ladder polysiloxanes,such as cage-like and irregular oligomers,and their effects on dielectric properties remain underexplored.In this study,a series of ladder-like polysiloxanes(X-TMS)with diverse side groups weresynthesized via a one-step base-catalyzed method.The influence of the benzocyclobutene(BCB)side groups on the formation of regular ladder structures was systematically investigated.Notably,BCB incorporation disrupted the structural regularity,favoring the formation of cage-like and irregular topologies,which were extensively characterized using 29silicon nuclear magnetic resonance spectroscopy(^(29)Si-NMR),Fourier transform infrared spectroscopy(FTIR),gel permeation chromatography(GPC),and X-ray diffraction(XRD).These structural defects were beneficial for improving the hydrophobicity and thermal stability.Copolymerization of X-TMS with commercial DVS-BCB resins further enhanced the mechanical properties,with the elastic modulus increasing from 3.6 GPa to 4.4 GPa and water absorption reduced from 0.33 wt%to 0.06 wt%.This study establishes a clear correlation between topological structures and material properties.These findings not only advance the understanding of the structure-property relationships in ladder polysiloxanes but also provide a novel approach for designing high-performance interlayer dielectric materials for next-generation microelectronics.展开更多
The combination of silicon carbide(SiC)ceramics and stereolithography technology shows promise for manufacturing complex-shaped SiC components,expanding application possibilities.However,high sintering temperature and...The combination of silicon carbide(SiC)ceramics and stereolithography technology shows promise for manufacturing complex-shaped SiC components,expanding application possibilities.However,high sintering temperature and structural-performance anisotropy limit the practical use of 3D-printed SiC components.Herein,a novel method is introduced to produce high-specific-strength SiC-based ceramics at a relatively low temperature of 1100℃.A mixed SiC/SiO_(2) slurry(30%SiO_(2) and 70%SiC by volume)with a solid loading of up to 40%was prepared to improve UV light penetration and printability.Additionally,incorporating a high content of methyl-phenyl-polysiloxane(PSO)solution(75%by weight)enabled low-temperature pyrolysis of SiC/SiO_(2)/PSO ceramics.The SiC/SiO_(2)/PSO ceramic lattices after pyrolysis achieved a specific strength as high as(1.03×10^(5))N·m·kg^(-1) and a density of 1.75 g·cm^(-3),outperforming similar SiC-based lattices structures of similar porosities.The bending strength of(95.49±8.79)MPa was comparable to that of ceramics sintered at 1400℃ or higher.Notably,the addition of the silicon carbide oxide(SiOC)phase reduced anisotropy,lowering the transverse and longitudinal compression strength ratios from 1.87 to 1.08,and improving mechanical properties by 79%.This improvement is attributed to SiOC shrinkage,promoting a uniform distribution of sintered components,resulting in a more robust and balanced material structure.This method offers valuable insight into the additive manufacturing(AM)of SiC-based ceramics at lower temperatures and provides new guidance for controlling anisotropy in 3D-printed ceramic parts.展开更多
Two types of polysiloxanes, which contain both C 60 moieties and carbazolyl groups in the side chains with a difference in the numbers of the reacting site on C 60 molecules, were synthesized and their fluor...Two types of polysiloxanes, which contain both C 60 moieties and carbazolyl groups in the side chains with a difference in the numbers of the reacting site on C 60 molecules, were synthesized and their fluorescent properties were studied to distinguish the role of C 60 in the luminescent polymers. Our results demonstrated that when C 60 moieties are bonded to the polymers as multisubstituents but not linked to the luminescent moieties directly, the luminescence of the resultant polymers were still very strong instead of quenching, even the substituted degree is only 1 01.展开更多
基金The project supported by the National Natural Science Foundationthe Doctoral Programme Foundation of Institution of Higher Education of China
文摘Side chain liquid crystalline golysiloxanes conta ing biphenyl and benzyl ether mesogen were synthesized by the hydrosilation of poly(methylhydrcsiloxane) with 4-(4-allyloxybenzytoxy)-4'- methoxybiphenyl(M_1),4-(4-allyloxybenzyloxy)-4'-ethoxybiphenyl(M_2),4-(4-allyloxybenzyloxy)-4'- propoxybiphenyl(M_3),4-(4-allyloxybenzyloxy)-4'-butoxybiphenyl(M_4),4-(4-allyloxybenzyloxy)-4'- pentyloxybiphenyl(M_5).The phase behavior of monomeric and polymeric liquid crystals was chararcterized by differential scanning calorimetry and optical polarization microscopy.Both the monomeric and polymeric liquid crystals exhibit liquid crystal behaviors.
文摘A new serial chiral side-chain liquid crystal polysiloxanes containing L-Tyr structures were synthesized at room temperature. Both of them exhibited Sc phase at room temperature.
文摘Two new stationary phases : (Ⅰ) [bikis(2,6-di-O-pentyl-3-O-hex-6O-pentyl-3-O-methyl)-β-CD-polysiloxane] and (Ⅱ) [heptkis(2,6-di-O-methyl-3-O-hex-6-enyl)-β-CD-polysiloxane] were synthesized and successfully used for GC separation of chiral isomers.The possess high column efficiency and exhibit fine chiral separation ability.
基金Funded by the Defense Pre-research Project of the"EleventhFive-Year-Plan"of China(51312040404)
文摘A series of elastomers , based on NBR , polysiloxanes （PS） were prepared and characterized by tensile tests, thermogravimetry （ TG ） and differential scanning calorimetry （ DSC ）. Two kinds of vulcanizing agent, DMDBH （2,5-dimethyl- 2,5-di （ t- butyl perory ） hexane ） and DCP （ dicumylperoxide ） were used to investigate the influence of different vulcanizing agents on properties of PS/ NBR. The addition of PS to NBR was found to improve the thermal stability and decrease the tensile strength of NBR. The tensile strength decreased conshterably while the elongation at break increased obviously with the increase of PS content. The series using DMDBH as vulcanizing agent showed a higher tensile strength and elongation at break than the series using DCP as vulcanizing agent. Simultaneity the thermal stability increased with the increase of PS content.
文摘New thermotropic chloro-bridged dinuclear palladium coordinating imine side chain liquid crystalline polysiloxanes have been synthesized. Their mesomorphic properties have been investigated by DSC, X-ray diffraction and polarizing microscopy. The polymeric complexes show nematicdiscotic (Nd) mesophase. It is found that the temperature range of liquid crystalline state of chloro- bridged polymeric complexes is much wider than that of acetato- bridged ones and imine side chain polysiloxane. This indicates that the disc-like chloro-bridged palladium complexing units play a role as mesogen in mesophase.
文摘A new type of β-diketone based side chain liquid crystalline polysiloxanes (DKLCP) with different length of flexible spacers and end groups have been synthesized by hydrosilation reaction. This is liquid crystal polymers (LCP) using coordinating β-diketone ligand as mesogens. The phase behaviour of DKLCP polymers was studied by differential scanning calorimetry and polarizing microscopy. X-ray diffraction investigations demonstrated that the polysiloxanes with sufficiently long flexible spacers were smectic liquid crystal polymers, while those with much shorter spacers were nematic ones.
基金supported by the National Natural Science Foundation of China(No.20874040)Research Funds from University of Jinan(XKY0721)
文摘Polyurethanes（PU） were prepared using toluene diisocyanate,polypropylene glycol,ethylene glycol, dimethylolpropionic acid and triethylamine,and a siloxane modified PU（PSU） was obtained through reaction of the PU prepolymers with bis（3-（1-methoxy-2-hydroxypropoxy）propyl） terminated polysiloxanes（PMTS） of different molecular weight,specifically designed for this purpose.Results showed that,with increases in molecular weight of PMTS and its content,viscosity of the final PSU latexes decreased;phase separation of the incorporated PMTS in PSU films increased;the average particle sizes of the latexes varied between 110 nm and 330 nm,and the surface tension in the final latexes was relatively constant regardless of PMTS amount and its molecular weight.It was likely that copolymerized polysiloxanes had trend to enrich on top of the film when PMTS molecular weight was around 2000 and its content above 5 wt%.In general, PMTS modified polyurethane films showed higher performance than those from unmodified waterborne polyurethane latexes.
基金This project was financially supported by the National Natural Science Foundation of China(Approved No.29775006)
文摘Two kinds of side chain liquid crystalline polysiloxanes containing crown ether and benzyl ether were synthesized and characterized by optical polarization microscopy. Both the monomeric liquid crystals and polymeric liquid crystals show smectic phases.
文摘A series of side chain liquid crystalline polysiloxanes containing either cholesteryl or cyanobiphenyl mesogenic groups were synthesized by the hydrosilylation reaction of a polysiloxane containing Si H group with a vinyl terminated compound containing the mesogenic group. Their chemical structures were confirmed by IR, 1H NMR, and elemental analysis, Their phase behaviors were investigated by differential scanning calorimetry, optical polarizing microscope, and X ray diffraction techniques. The results show that all these polysiloxanes except PⅤ display smectic or nematic mesonorphism or both. The dependence of phase transition temperature on the rigidity of mesogenic unit. the length of spacer group, and the flexibility of Si(CH 3) 2O chain is also described.
基金Supported by the Fund for Ph.D. programme from State Education Commission
文摘The present paper represents the syntheses of polypropyloxymethyldithia 15-crown-5 and 18-crown-6 supported on silica and their platinum complexes. The platinum complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The influences of temperature, amount of platinum complexes used and the nature of olefins used on the catalytic activity of the complexes are also investigated in this paper.
文摘A novel kind of multifunctional polysiloxane containing charge-transporting agent and as electro-optical chromophore has been prepared for photorefractive application. The structural characterization of this kind of polymer is presented by IR spectra and elemental analysis.
基金The project was financially supported by the National Natural Science Foundation of China (Grant 29573115).
文摘Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes have been prepared from C-60 via amination with omega-decenylamine, followed by hydrosilylation with triethoxysilane and immobilization on fumed silica or by hydrosilylation with methyldichlorosilane and polycondensation with polydimethylsiloxanol, and then by reacting them with potassium chloroplatinite or rhodium chloride in acetone respectively under argon atmosphere. It was found that the four noble metal complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The regioselectivity of platinum complexes for styrene increases remarkably by introducing C-60 moiety. Factors influencing catalytic activity and the mechanism have been investigated.
基金This project was financially supported by the National Natural Science Foundation of China (Approved No.29775006)
文摘Side chain liquid crystalline polysiloxanes containing benzyl ether linkingunits were synthesized by the hydrosilylation of poly (methylhydrosiloxane) with a series of4-(4-alkoxybenzyloxy)-4'-allyloxybiphenyl monomers [4-(4-methoxybenzyloxy )-4'-allyloxy-biphenyl(M_1), 4-(4-ethoxybenzyloxy)-4'-allyloxybiphenyl (M_2), 4-(4-propoxybenzyloxy)-4'-allyloxybiphenyl (M_3), 4-(4-butoxybenzyloxy)-4'-allylox(M_4), 4-(4-pentoxy-benzyloxy)-4'-allyloxybiphenyl (M_5), 4-benzyloxy-4'-allyloxybiphenyl (M_6)]. The phasebehavior of monomeric and polymeric liquid crystals was characterized by differential scan-ning calorimetry and optical polarization microscopy where the groups are ranged frommethoxy to pentoxy Both the monomeric and polymeric liquid crystals exhibit 1iquidcrystal behaviors.
基金This work was supported by the National Natural Science Foundation of China.
文摘A variety of mesomorphic side-chain polysiloxanes were synthesized by using hydrosilylation reaction with dicyclopentadienylplatinum(II) (DPPC) as the catalyst. The mesogenic groups are derivatives of stilbene with cyano or nitro tail groups. The products were characterized by DSC, X-ray diffraction and polarizing optical microscopy (POM). All the polymers were found to have relatively low T-g and can form a smectic liquid crystal phase.
文摘The comparison between physical properties and chemical structures of several polysiloxanes was studied at initial state and upon ageings. Techniques such as densimetry, gel permeation chromatography, FTIR spectroscopy, thermogravim- etric analysis coupled with IR spectroscopy and the new tool photo-DSC were used to give assessments of average mo- lecular weight, chemical evolution, cristallinity and thermal stability. Different types of ageing such as thermal ageing (60?C and 100?C), photo-ageing and acid vapour ageing were performed. After ageing we observed an evolution of chemical structures and physical properties for all samples. The main pathway of degradation is given for each sample. It results in oxidation, chain scission or cross-linking. Cross-linking levels are dependant on the type of ageing, the chemical structure and the initial rate of cristallinity. Cross-linking reactions are favoured after photo-ageing. Oxidation is higher for polysiloxane with aliphatic carbon chain.
基金supported by the National Natural Science Foundation of China(Grants 51373179,51073163,51803218,and 51373184).
文摘Nonconventional fluorescent materials,which are nonaromatic or consist of isolated aromatic systems,have attracted extensive attention because of their aggregation-induced emission properties.The mechanism of nonconventional fluorescence remains incompletely understood,hindering the prediction and modulation of its emission color.Achieving full-color tunability in such systems,particularly within elastomers,is highly challenging.Herein,fluorescent cross-linked polysiloxanes are synthesized using aliphatic amino-terminated polysiloxane and glutaraldehyde,exhibiting full-color emission that can be continuously tuned through thermal treatments within a single material system.Thermal treatment of cross-linked polysiloxanes enables precise control over the structural evolution of fluorophores from imines to 3-(2-piperidyl)pyridinium derivatives and their aggregation states.It enables the continuous and wide-range modulation of the emission color.Additionally,the intramolecular and intermolecular charge transfers of the novel unconventional fluorophore,3-(2-piperidyl)pyridinium derivatives,have been identified,which are of great significance for aggregation-induced bathochromic fluorescence.Prepared from all commercial chemicals,these cross-linked polysiloxanes show great potential for large-scale production and applications,especially as flexible fluorescent light-conversion layers and solvent-responsive smart materials.Furthermore,our research is expected to inspire the innovation of unconventional fluorophores in multiple dimensions.
基金Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110540Key Research and Development Program of Shaanxi,Grant/Award Number:2022SF-599+1 种基金Fundamental Research Funds for the Central Universities,Grant/Award Number:D5000230114National Natural Science Foundation of China,Grant/Award Number:22175143。
文摘Nonconventional luminescent materials have been rising stars in organic luminophores due to their intrinsic characteristics,including water-solubility,biocompatibility,and environmental friendliness and have shown potential applications in diverse fields.As an indispensable branch of nonconventional luminescent materials,polysiloxanes,which consist of electron-rich auxochromic groups,have exhibited outstanding photophysical properties due to the unique silicon atoms.The flexible Si-O bonds benefit the aggregation,and the empty 3d orbitals of Si atoms can generate coordination bonds including N→Si and O→Si,altering the electron delocalization of the material and improving the luminescent purity.Herein,we review the recent progress in luminescent polysiloxanes with different topologies and discuss the challenges and perspectives.With an emphasis on the driving force for the aggregation and the mechanism of tuned emissions,the role of Si atoms played in the nonconventional luminophores is highlighted.This review may provide new insights into the design of nonconventional luminescent materials and expand their further applications in sensing,biomedicine,lighting devices,etc.
基金financially supported by the National Natural Science Foundation of China(Nos.52373316,22075298,and52373020)the Beijing Municipal Natural Science Foundation(No.2212053)。
文摘Low dielectric constant(low-k)materials are critical for advanced packaging in high-density microelectronic devices and high-frequency communication technologies.Ladder polysiloxanes,which are characterized by their unique double-chain structure and intrinsic microporosity,offer remarkable advantages in terms of thermal stability,oxidation resistance,and dielectric performance.However,structural defects in ladder polysiloxanes,such as cage-like and irregular oligomers,and their effects on dielectric properties remain underexplored.In this study,a series of ladder-like polysiloxanes(X-TMS)with diverse side groups weresynthesized via a one-step base-catalyzed method.The influence of the benzocyclobutene(BCB)side groups on the formation of regular ladder structures was systematically investigated.Notably,BCB incorporation disrupted the structural regularity,favoring the formation of cage-like and irregular topologies,which were extensively characterized using 29silicon nuclear magnetic resonance spectroscopy(^(29)Si-NMR),Fourier transform infrared spectroscopy(FTIR),gel permeation chromatography(GPC),and X-ray diffraction(XRD).These structural defects were beneficial for improving the hydrophobicity and thermal stability.Copolymerization of X-TMS with commercial DVS-BCB resins further enhanced the mechanical properties,with the elastic modulus increasing from 3.6 GPa to 4.4 GPa and water absorption reduced from 0.33 wt%to 0.06 wt%.This study establishes a clear correlation between topological structures and material properties.These findings not only advance the understanding of the structure-property relationships in ladder polysiloxanes but also provide a novel approach for designing high-performance interlayer dielectric materials for next-generation microelectronics.
基金financially supported by the Key Project of Department of Education of Guangdong Province(Grant No.2022ZDZX3017)Special Support Plan of Guangdong Province(Grant No.2021TQ05Z151)+2 种基金Guangdong Basic and Applied Basic Research Foundation(Grant No.2024A1515010049)SZU Research Fund(Grant No.GFPY-YB-2024-03)Shenzhen Science and Technology Programs(Grant Nos.GJHZ20210705141803011 and 20200731211324001).
文摘The combination of silicon carbide(SiC)ceramics and stereolithography technology shows promise for manufacturing complex-shaped SiC components,expanding application possibilities.However,high sintering temperature and structural-performance anisotropy limit the practical use of 3D-printed SiC components.Herein,a novel method is introduced to produce high-specific-strength SiC-based ceramics at a relatively low temperature of 1100℃.A mixed SiC/SiO_(2) slurry(30%SiO_(2) and 70%SiC by volume)with a solid loading of up to 40%was prepared to improve UV light penetration and printability.Additionally,incorporating a high content of methyl-phenyl-polysiloxane(PSO)solution(75%by weight)enabled low-temperature pyrolysis of SiC/SiO_(2)/PSO ceramics.The SiC/SiO_(2)/PSO ceramic lattices after pyrolysis achieved a specific strength as high as(1.03×10^(5))N·m·kg^(-1) and a density of 1.75 g·cm^(-3),outperforming similar SiC-based lattices structures of similar porosities.The bending strength of(95.49±8.79)MPa was comparable to that of ceramics sintered at 1400℃ or higher.Notably,the addition of the silicon carbide oxide(SiOC)phase reduced anisotropy,lowering the transverse and longitudinal compression strength ratios from 1.87 to 1.08,and improving mechanical properties by 79%.This improvement is attributed to SiOC shrinkage,promoting a uniform distribution of sintered components,resulting in a more robust and balanced material structure.This method offers valuable insight into the additive manufacturing(AM)of SiC-based ceramics at lower temperatures and provides new guidance for controlling anisotropy in 3D-printed ceramic parts.
文摘Two types of polysiloxanes, which contain both C 60 moieties and carbazolyl groups in the side chains with a difference in the numbers of the reacting site on C 60 molecules, were synthesized and their fluorescent properties were studied to distinguish the role of C 60 in the luminescent polymers. Our results demonstrated that when C 60 moieties are bonded to the polymers as multisubstituents but not linked to the luminescent moieties directly, the luminescence of the resultant polymers were still very strong instead of quenching, even the substituted degree is only 1 01.
